阅读说明：本技术 一种多孔氮化硅陶瓷表面涂层的结构及制备方法 (Structure and preparation method of porous silicon nitride ceramic surface coating ) 是由 王超 刘会超 张帆 白宇 王昱征 吴玉胜 王占杰 于 2021-09-27 设计创作，主要内容包括：一种多孔氮化硅陶瓷表面涂层的结构及制备方法,在多孔氮化硅陶瓷基体表面设置有涂层,该涂层包括：混合料浆内层和外层粉体层；混合料浆内层为软相BN纳米片与硬相陶瓷粉体颗粒混合料浆；外层粉体层为玻璃粉体料浆。陶瓷粉体为α-Si-(3)N-(4)和SiO-(2)。外层的玻璃粉体是B-Si-Al-O和Y-Si-Al-O玻璃粉体。通过对BN纳米片与陶瓷颗粒表面进行修饰,通过自组装使大量BN纳米片和陶瓷颗粒的均匀混合,再通过反应熔渗技术形成软相BN纳米片与硬相陶瓷颗粒相结合的贝壳珍珠层仿生结构复合陶瓷涂层,所制备的涂层具有防水性能好、力学性能优异、抗热冲击能力强等优异的性能。(A porous silicon nitride ceramic surface coating structure and a preparation method thereof are provided, wherein a coating is arranged on the surface of a porous silicon nitride ceramic substrate, and the coating comprises: mixing the inner layer and the outer layer of powder of the slurry; the inner layer of the mixed slurry is soft-phase BN nanosheet and hard-phase ceramic powder particle mixed slurry; the outer powder layer is glass powder slurry. The ceramic powder is alpha-Si 3 N 4 And SiO 2 . The outer layer of glass powder is B-Si-Al-O and Y-Si-Al-O glass powder. The BN nano sheets and the surface of the ceramic particle are modified, a large number of BN nano sheets and ceramic particles are uniformly mixed through self-assembly, and a shell pearl layer bionic structure composite ceramic coating combining soft-phase BN nano sheets and hard-phase ceramic particles is formed through a reaction infiltration technology.)

1. The utility model provides a porous silicon nitride ceramic surface coating's structure, is provided with the coating on porous silicon nitride ceramic matrix surface, its characterized in that: the coating is a shell pearl layer bionic structure formed by combining soft-phase BN nanosheets and hard-phase ceramic particles.

2. The porous silicon nitride ceramic surface coating structure of claim 1, wherein: the ceramic particles are alpha-Si₃N₄And SiO₂。

3. A method of preparing a porous silicon nitride ceramic surface coating structure according to claim 1, characterized in that: the method comprises the following steps:

step 1, matrix treatment: selecting porous silicon nitride ceramics as a matrix, grinding the porous silicon nitride ceramics by using 600-1000-mesh sand paper until the surface of the matrix is smooth and flat, then putting the ground porous silicon nitride ceramics into deionized water, ultrasonically cleaning for 15-30min, putting the cleaned porous silicon nitride ceramics into an oven after twice cleaning, and drying for 10-12h at 70-80 ℃;

step 2, modifying BN nanosheets: mixing BN nano-sheets and a sodium hydroxide aqueous solution, stirring and ultrasonically oscillating for 1 h; and (3) putting the mixed solution into a reaction kettle, carrying out hydrothermal reaction for 12h at 120 ℃, washing the solution to a certain pH value, carrying out vacuum filtration, and drying the pumped and filtered powder for 12h at 60 ℃ to obtain a modified BN nanosheet product.

Step 3, ceramic powder modification: adding the ceramic powder into a mixed solution of ethanol and deionized water, carrying out ultrasonic treatment at room temperature for 15-30min, adding a silane coupling agent, carrying out ultrasonic oscillation for 15-30min, stirring for 10-12h, washing the product after uniform stirring and mixing, washing to a certain pH value, carrying out vacuum filtration to obtain a final product, and drying the final product at 60-80 ℃ for 12-24h to obtain a modified ceramic powder product.

Step 4, preparing slurry: mixing the modified BN nanosheets with deionized water, and stirring for 1h to obtain BN nanosheet slurry; and simultaneously mixing the modified ceramic powder with deionized water, and stirring for 1h to obtain ceramic powder slurry. And then, dropwise adding the BN nanosheet slurry into the ceramic powder slurry, stirring for 1-2h, and ultrasonically oscillating for 30-60min to fully mix the BN nanosheet slurry and the ceramic powder slurry to prepare the mixed slurry of the BN nanosheet/ceramic powder. Mixing the glass powder with deionized water, stirring for 2h, and performing ultrasonic oscillation for 30min to obtain glass powder slurry.

Step 5, preparing a double-layer powder layer on the surface of the porous silicon nitride ceramic: firstly, coating the prepared mixed slurry on a pretreated porous silicon nitride substrate to form an inner powder layer; and then coating the glass powder slurry on the surface of the inner layer powder layer to form an outer layer glass powder layer. Thereafter, the mixture was dried at 60 ℃ for 30min to obtain a double-layered powder layer.

And 6, sintering a sample: placing the dried sample into an atmosphere sintering furnace for sintering, wherein the sintering temperature is 1450-₂The atmosphere pressure was 0.1 MPa.

4. The method for preparing a porous silicon nitride ceramic surface coating structure according to claim 3, wherein: the porosity of the porous silicon nitride ceramic matrix in the step 1 is 30-60%.

5. The method for preparing a porous silicon nitride ceramic surface coating structure according to claim 3, wherein: the concentration of the sodium hydroxide aqueous solution in the step 2 is 5mol/L, and the mass ratio of the BN nanosheet to the sodium hydroxide is 1: 20, the pH of the resulting solution was 9.

6. The method for preparing a porous silicon nitride ceramic surface coating structure according to claim 3, wherein: the volume ratio of the ethanol mixed with the deionized water in the step 3 is 98: 2; the solid content of the added ceramic powder is 4 percent, the content of the silane coupling agent is 0.38 percent by weight, and the PH value of the obtained solution is 3.8 to 4.2.

7. The method for preparing a porous silicon nitride ceramic surface coating structure according to claim 3, wherein: and 4, the solid content of the BN nanosheet slurry is 0.09%, the solid content of the ceramic powder slurry is 0.99%, the volume ratio of the BN nanosheets to the ceramic powder in the mixed slurry is 3/97-10/90, and the solid content of the glass powder slurry is 10%.

8. The method for preparing a porous silicon nitride ceramic surface coating structure according to claim 3, wherein: and 4, the glass powder is B-Si-Al-O and Y-Si-Al-O glass powder.

9. The method for preparing a porous silicon nitride ceramic surface coating structure according to claim 3, wherein: 5, preparing a mixed slurry with soft-phase BN nanosheet and hard-phase ceramic powder particles as an inner layer; the outer glass powder layer is glass powder slurry.

Technical Field

The invention belongs to the technical field of preparation of ceramic coatings, and relates to a method for preparing a bionic structure ceramic coating on the surface of a porous silicon nitride ceramic matrix.

Background

The porous silicon nitride ceramic material is prepared by high-temperature sintering, contains more communicated or closed air holes in the ceramic material, has the advantages of common ceramic materials such as high melting point, high hardness, high wear resistance, corrosion resistance and the like, has excellent mechanical, physical and chemical properties such as small specific gravity, small thermal conductivity, small elastic modulus and the like, is a good structural and functional integrated material, and can be used as a heat insulation material, a wave transmission material and the like. However, due to the existence of the air holes, the porous ceramic is extremely easy to absorb moisture, and after absorbing surrounding water vapor, the electrical property and the heat insulation capability of the porous ceramic are seriously influenced. In addition, the porous structure causes the reduction of the mechanical properties of the material, thereby reducing the erosion resistance and the wear resistance of the material, so that the material is greatly limited in the practical application process.

Aiming at the problems of the porous ceramic in practical use, a layer of compact ceramic coating needs to be prepared on the surface of the porous ceramic to isolate water vapor in the environment and improve the mechanical property of the porous ceramic. At present, the existing coating preparation methods include a chemical vapor deposition method, a sol-gel method, a plasma spraying method, a pressureless sintering method and the like. Chemical Vapor Deposition (CVD) is a technique for depositing solid films on the surface of a substrate by spatial vapor phase chemical reaction. Preparing compact Si on the surface of porous nitride ceramic by CVD method₃N₄After coating, the coating has high mechanical strength, good rain erosion resistance and sand erosion resistance. In China, some researchers also adopt CVD method to prepare Si on the surface of porous nitride ceramics₃N₄The prepared coating has a uniform and compact structure, not only plays a good role in moisture resistance, but also obviously improves the mechanical property of the porous nitride ceramic. However, Si prepared by CVD₃N₄The coating is typically amorphous Si₃N₄Phase, the toughness and high temperature stability of the coating are poor, resulting in a coatingHas poor thermal shock resistance. The sol-gel method is a sol-gel-solid coating conversion process, ester compounds or metal alkoxide are dissolved in an organic solvent, the mixture is uniformly mixed and undergoes hydrolysis or polycondensation reaction to form a stable sol system, the solvent is evaporated to form gel, and the gel is dried and thermally treated to form the required coating on the surface of a substrate. Porous Si after sol-gel process of preparing coating₃N₄The water absorption rate is obviously reduced, and the strength is obviously improved. Although sol-gel processes can produce dense vitreous coatings on porous ceramic surfaces, they tend to be less resistant to thermal shock. The plasma spraying particle rapid deposition process is a non-equilibrium thermodynamic process, and particles in a semi-molten state can be rapidly cooled to form a ceramic coating after deposition. However, this method causes a large amount of amorphous phase to exist in the coating layer, and causes a large residual stress in the coating layer, which makes the coating layer surface susceptible to defects such as microcracks. This will affect the compactness of the coating as well as the mechanical properties of the coating. In addition, some researchers have used pressureless sintering to produce vitreous coatings on porous silicon nitride surfaces. The coating has good erosion resistance, high-temperature strength and high-temperature broadband wave-transmitting stability, but the coating has weak thermal shock resistance, and a large amount of penetrating cracks can be generated on the coating after 5 times of thermal shock at the temperature of 1000 ℃, so that the water vapor isolation effect and the mechanical property of the coating are obviously reduced. Therefore, the existing coatings can not meet the use requirements under high-temperature extreme environments.

The BN nanosheet is a flexible, ultra-light, super-strong, high-elasticity and high-heat-conduction material due to the two-dimensional planar structure similar to graphene, and is commonly used for modifying the mechanical property and the thermal property of a ceramic material. Some researchers prepare ceramic matrix composite materials with good chemical properties by doping BN nano-sheets into silicon carbide ceramics, and when 1 wt% of BN nano-sheets are added, the bending strength of the composite SiC ceramic material reaches 507MPa and is improved by 123%; the fracture toughness reaches 5.41 MPa.m^1/2The improvement is 41.6%. More researches show that the BN nano-sheet is added into the composite ceramic coating as a reinforcing phase to improve the comprehensive performance of the composite ceramic coatingIs completely realizable; when the silicon nitride/BN nanosheet composite ceramic is pressureless sintered, the porosity, strength and Young's modulus of the silicon nitride ceramic composite material are increased along with the increase of the content of boron nitride, and the thermal shock critical temperature difference is increased by adding BN. Therefore, the BN nano-sheet is introduced into the ceramic coating, so that the mechanical property and the thermal shock resistance of the coating can be greatly improved, and the requirement of stable use of the porous silicon nitride ceramic in an extreme environment is met. However, the BN nanosheets have the problems of easy agglomeration and difficult dispersion, so that the properties of the ceramic material can be modified only by a small amount of doping, and the improvement range of the strength, the fracture toughness and the thermal conductivity of the coating material is limited.

Disclosure of Invention

Object of the Invention

The invention provides a structure of a porous silicon nitride ceramic surface coating and a preparation method thereof, aiming at the problems of insufficient strength, poor fracture toughness, poor thermal conductivity and the like of coating materials.

Technical scheme

A porous silicon nitride ceramic surface coating structure is provided with a coating on the surface of a porous silicon nitride ceramic substrate, and the coating is characterized in that: the coating is a shell pearl layer bionic structure formed by combining soft-phase BN nanosheets and hard-phase ceramic particles.

The ceramic particles are alpha-Si₃N₄And SiO₂。

A preparation method of a porous silicon nitride ceramic surface coating comprises the following steps:

step 1, matrix treatment: selecting porous silicon nitride ceramics as a matrix, grinding the porous silicon nitride ceramics by using 600-1000-mesh sand paper until the surface of the matrix is smooth and flat, then putting the ground porous silicon nitride ceramics into deionized water, ultrasonically cleaning for 15-30min, putting the cleaned porous silicon nitride ceramics into an oven after twice cleaning, and drying for 10-12h at 70-80 ℃.

The porosity of the porous silicon nitride ceramic matrix is 30-60%.

Step 2, modifying BN nanosheets: mixing BN nano-sheets and a sodium hydroxide aqueous solution, stirring and ultrasonically oscillating for 1 h; and (3) putting the mixed solution into a reaction kettle, carrying out hydrothermal reaction for 12h at 120 ℃, washing the solution to a certain pH value, carrying out vacuum filtration, and drying the pumped and filtered powder for 12h at 60 ℃ to obtain a modified BN nanosheet product.

The concentration of the sodium hydroxide aqueous solution is 5mol/L, and the mass ratio of the BN nanosheet to the sodium hydroxide is 1: 20, the pH of the resulting solution was 9.

Step 3, ceramic powder modification: adding the ceramic powder into a mixed solution of ethanol and deionized water, carrying out ultrasonic treatment at room temperature for 15-30min, adding a silane coupling agent, carrying out ultrasonic oscillation for 15-30min, stirring for 10-12h, washing the product after uniform stirring and mixing, washing to a certain pH value, carrying out vacuum filtration to obtain a final product, and drying the final product at 60-80 ℃ for 12-24h to obtain a modified ceramic powder product.

The volume ratio of the ethanol to the deionized water is 98: 2; the solid content of the added ceramic powder is 4 percent, the content of the silane coupling agent is 0.38 percent by weight, and the PH value of the obtained solution is 3.8 to 4.2.

Step 4, preparing slurry: mixing the modified BN nanosheets with deionized water, and stirring for 1h to obtain BN nanosheet slurry; and simultaneously mixing the modified ceramic powder with deionized water, and stirring for 1h to obtain ceramic powder slurry. And then, dropwise adding the BN nanosheet slurry into the ceramic powder slurry, stirring for 1-2h, and ultrasonically oscillating for 30-60min to fully mix the BN nanosheet slurry and the ceramic powder slurry to prepare the mixed slurry of the BN nanosheet/ceramic powder. Mixing the glass powder with deionized water, stirring for 2h, and performing ultrasonic oscillation for 30min to obtain glass powder slurry.

The solid content of the BN nanosheet slurry is 0.09%, the solid content of the ceramic powder slurry is 0.99%, and the volume ratio of the BN nanosheets to the ceramic powder in the mixed slurry is 3/97-10/90; the glass powder is B-Si-Al-O and Y-Si-Al-O glass powder, and the solid content of the glass powder slurry is 10%.

Step 5, preparing a double-layer powder layer on the surface of the porous silicon nitride ceramic: firstly, coating the prepared mixed slurry on a pretreated porous silicon nitride substrate to form an inner powder layer; and then coating the glass powder slurry on the surface of the inner powder layer to form an outer powder layer. Thereafter, the mixture was dried at 60 ℃ for 30min to obtain a double-layered powder layer.

The inner layer of the mixed slurry is mixed slurry of soft-phase BN nanosheets and hard-phase ceramic powder particles; the outer glass powder layer is glass powder slurry.

And 6, sintering a sample: placing the dried sample into an atmosphere sintering furnace for sintering, wherein the sintering temperature is 1450-₂The atmosphere pressure was 0.1 MPa.

Advantages and effects

The invention provides a structure of a porous silicon nitride ceramic surface coating and a preparation method thereof. According to the method, the BN nanosheets and the surface of the ceramic particle are modified, a large number of BN nanosheets and the ceramic particle are uniformly mixed through self-assembly, and the shell pearl layer bionic structure composite ceramic coating combining the soft-phase BN nanosheets and the hard-phase ceramic particle is formed through a reaction infiltration technology.

Compared with the prior art, the method has the following advantages: (1) the method has the advantages of simple process, low cost, uniform coating, no limitation of the size and the shape of a matrix and the like. Therefore, the process is very suitable for preparing the ceramic coating on the surface of the porous silicon nitride ceramic with a complex shape. (2) In the bionic structure coating, the high-strength and high-toughness BN nanosheets can generate toughening mechanisms such as crack deflection, bridging, microcrack branching and the like to improve the mechanical property of the coating, and meanwhile, the high thermal conductivity of the BN nanosheets is utilized to improve the thermal conductivity of the coating. Thereby improving the thermal shock resistance of the coating. (3) The preparation method reduces the agglomeration phenomenon of the BN nanosheet and can obtain the bionic structure ceramic coating with a uniform structure.

Drawings

FIG. 1 shows BNNSs/α -Si₃N₄The surface appearance of the/Y-Si-Al-O base ceramic coating;

FIG. 2 shows BNNSs/α -Si₃N₄The cross-sectional shape of the/Y-Si-Al-O based ceramic coating.

Detailed Description

The invention is further described below with reference to the accompanying drawings:

a porous silicon nitride ceramic surface coating structure is provided, wherein a coating is arranged on the surface of a porous silicon nitride ceramic matrix, and the porosity of the porous silicon nitride ceramic matrix is 30-60%. The coating comprises: the coating is a shell pearl layer bionic structure formed by combining soft-phase BN nanosheets and hard-phase ceramic particles. The ceramic particles are alpha-Si₃N₄And SiO₂。

A preparation method of a porous silicon nitride ceramic surface coating structure comprises the following steps: firstly, modifying the surfaces of BN nano sheets and ceramic particles, and forming mixed slurry of the BN nano sheets and the ceramic particles through self-assembly; then brushing mixed slurry of BN nano sheets and ceramic particles on the surface of the porous silicon nitride ceramic substrate to serve as an inner-layer powder layer, brushing a layer of glass powder slurry on the basis of the inner-layer powder layer to serve as an outer-layer powder layer, forming a liquid phase on the outer layer through high temperature, infiltrating the liquid phase into the inner-layer powder layer, promoting sintering of inner-layer powder, and forming a compact coating; the ceramic coating with the structure has good waterproof performance and mechanical performance, and the hardness, the thermal conductivity and the thermal shock resistance of the porous silicon nitride substrate are improved.

Example 1

This example is to prepare BNNSs/alpha-Si on the surface of porous silicon nitride ceramic substrate₃N₄the/Y-Si-Al-O bionic structure ceramic coating comprises the following steps:

step 1, matrix treatment: selecting porous silicon nitride with porosity of 50% as a substrate, using 600-mesh, 800-mesh and 1000-mesh sand paper to gradually and finely grind the porous silicon nitride until the surface of the substrate is smooth and flat, then placing the finely ground porous silicon nitride ceramic substrate into deionized water to perform ultrasonic cleaning for 30min, and drying for 10h at 80 ℃ after cleaning twice;

step 2, modifying BN nanosheets: mixing a BN nano sheet and a sodium hydroxide aqueous solution, wherein the concentration of the sodium hydroxide aqueous solution is 5mol/L, and the mass ratio of the BN nano sheet to the sodium hydroxide is 1: 20, stirring and ultrasonically oscillating for 1 h; and (3) putting the mixed solution into a reaction kettle, carrying out hydrothermal reaction for 12h at 120 ℃, carrying out vacuum filtration on the washing solution with the pH value of 9, and drying the pumped and filtered powder at 60 ℃ for 12h to obtain a modified BN nanosheet product.

Step 3, ceramic powder modification: adding ceramic powder into ethanol and deionized water according to a volume ratio of 98: 2, carrying out ultrasonic treatment at room temperature for 30min, adding a silane coupling agent with the content of 0.38 wt%, carrying out ultrasonic oscillation for 15min, stirring for 10h, uniformly stirring and mixing, washing the product, carrying out vacuum filtration to obtain a final product, and drying the final product at 60 ℃ for 24h to obtain the modified ceramic powder product.

Step 4, preparing slurry: mixing the modified BN nanosheet with deionized water, wherein the solid content is 0.09%, and stirring for 1h to obtain BN nanosheet slurry; and simultaneously mixing the modified ceramic powder with deionized water, wherein the solid content is 0.99%, and stirring for 1h to obtain ceramic powder slurry. Then, dropwise adding the BN nanosheet slurry into the ceramic powder slurry, stirring for 1h, and ultrasonically oscillating for 60min to fully mix the BN nanosheet slurry and the ceramic powder, wherein the volume ratio of the BN nanosheet to the ceramic powder in the mixed slurry is 5: and 95, preparing mixed slurry of the BN nanosheet/ceramic particles. Mixing glass powder with deionized water, wherein the solid content is 10%, stirring for 2h, and performing ultrasonic oscillation for 30min to obtain glass powder slurry.

Step 5, preparing a double-layer powder layer on the surface of the porous silicon nitride ceramic: firstly, coating the prepared mixed slurry on a pretreated porous silicon nitride ceramic substrate to form an inner powder layer; and then coating the glass powder slurry on the surface of the inner powder layer to form an outer powder layer. Then, the mixture was dried at 60 ℃ for 30min to obtain a double-layered powder layer.

And 6, sintering a sample: putting the dried sample into an atmosphere sintering furnace for sintering, wherein the sintering temperature is 1550 ℃, the heat preservation time is 1h, and the sintering atmosphere is N₂The atmosphere pressure was 0.1 MPa. The heating rate below 1000 ℃ is 15 ℃/min, the heating and cooling rates above 1000 ℃ are both 5 ℃/min, and the temperature is cooled along with the furnace after heat preservation until the temperature is cooled to the room temperature.

BNNSs/α -Si prepared in this example₃N₄the/Y-Si-Al-O ceramic coating is compact, the combination between interfaces is firm, and the thickness of the coating is about 150 mu m. After the coating is prepared by determination, the water absorption of the porous silicon nitride ceramic is reduced by 89%, the fracture toughness is obviously increased and reaches 6.12 MPa.m^1/2And after the composite coating is thermally shocked for 10 times at 1100 ℃, the coating still has good waterproof performance and mechanical property, the water absorption rate is only increased from 5.3 percent to 7.2 percent, the hardness value is 6.03GPa, the residual hardness ratio is up to 88.9 percent, and the thermal shock resistance is obviously improved.

Example 2

In this example, BNNSs/SiO was prepared on the surface of porous silicon nitride ceramic substrate₂the/B-Si-Al-O bionic structure ceramic coating comprises the following steps:

step 1, matrix treatment: selecting porous silicon nitride with porosity of 60% as a matrix, using 600-mesh, 800-mesh and 1000-mesh sand paper to gradually and finely grind the porous silicon nitride until the surface of the matrix is smooth and flat, then placing the finely ground porous silicon nitride ceramic matrix into deionized water to perform ultrasonic cleaning for 30min, and drying for 12h at 80 ℃ after cleaning twice;

step 2, modifying BN nanosheets: mixing a BN nano sheet and a sodium hydroxide aqueous solution, wherein the concentration of the sodium hydroxide aqueous solution is 5mol/L, and the mass ratio of the BN nano sheet to the sodium hydroxide is 1: 20, stirring and ultrasonically oscillating for 1 h; and (3) putting the mixed solution into a reaction kettle, carrying out hydrothermal reaction for 12h at 120 ℃, washing the pH value of the solution to 9, carrying out vacuum filtration, and drying the pumped and filtered powder for 12h at 60 ℃ to obtain a modified BN nanosheet product.

Step 3, ceramic powder modification: adding ceramic powder into ethanol and deionized water according to a volume ratio of 98: 2, carrying out ultrasonic treatment at room temperature for 30min, adding a silane coupling agent with the content of 0.38 wt%, carrying out ultrasonic oscillation for 30min, stirring for 10h, uniformly stirring and mixing, washing the product, carrying out vacuum filtration to obtain a final product, and drying the final product at 70 ℃ for 20h to obtain the modified ceramic powder product.

Step 4, preparing slurry: mixing the modified BN nanosheet with deionized water, wherein the solid content is 0.09%, and stirring for 1h to obtain BN nanosheet slurry; and simultaneously mixing the modified ceramic powder with deionized water, wherein the solid content is 0.99%, and stirring for 1h to obtain ceramic powder slurry. Then, dropwise adding the BN nanosheet slurry into the ceramic powder slurry, stirring for 2 hours, and ultrasonically oscillating for 30 minutes to fully mix the BN nanosheet slurry and the ceramic powder, wherein the volume ratio of the BN nanosheet to the ceramic powder in the mixed slurry is 10: and 90, preparing mixed slurry of the BN nanosheet/ceramic particles. Mixing glass powder with deionized water, wherein the solid content is 10%, stirring for 2h, and performing ultrasonic oscillation for 30min to obtain glass powder slurry.

Step 5, preparing a double-layer powder layer on the surface of the porous silicon nitride ceramic: firstly, coating the prepared mixed slurry on a pretreated porous silicon nitride ceramic substrate to form an inner powder layer; and then coating the glass powder slurry on the surface of the inner powder layer to form an outer powder layer. Then, the mixture was dried at 60 ℃ for 30min to obtain a double-layered powder layer.

And 6, sintering a sample: putting the dried sample into an atmosphere sintering furnace for sintering, wherein the sintering temperature is 1500 ℃, the heat preservation time is 1h, and the sintering atmosphere is N₂The atmosphere pressure was 0.1 MPa. The heating rate below 1000 ℃ is 15 ℃/min, the heating and cooling rates above 1000 ℃ are both 5 ℃/min, and the temperature is cooled along with the furnace after heat preservation until the temperature is cooled to the room temperature.

BNNSs/SiO prepared in this example₂the/B-Si-Al-O ceramic coating is compact and has firm interface bonding, and the thickness of the coating is about 130 mu m. After the coating is prepared by determination, the water absorption of the porous silicon nitride ceramic is reduced by 80 percent, the fracture toughness is obviously increased and reaches 5.98 MPa.m^1/2And after the composite coating is thermally shocked for 10 times at 1100 ℃, the coating still has good waterproof performance and mechanical property, the water absorption rate is only increased from 5.3 percent to 8.6 percent, the hardness value is 5.97GPa, and the thermal shock resistance is obviously improved.

Example 3

This example is to prepare BNNSs/alpha-Si on the surface of porous silicon nitride ceramic substrate₃N₄the/B-Si-Al-O bionic structure ceramic coating comprises the following componentsThe method comprises the following steps:

step 1, matrix treatment: selecting porous silicon nitride with porosity of 30% as a substrate, using 600-mesh, 800-mesh and 1000-mesh sand paper to gradually and finely grind the porous silicon nitride until the surface of the substrate is smooth and flat, then putting the finely ground porous silicon nitride ceramic substrate into deionized water, ultrasonically cleaning for 15min, and drying for 12h at 70 ℃ after cleaning twice;

step 2, modifying BN nanosheets: mixing a BN nano sheet and a sodium hydroxide aqueous solution, wherein the concentration of the sodium hydroxide aqueous solution is 5mol/L, and the mass ratio of the BN nano sheet to the sodium hydroxide is 1: 20, stirring and ultrasonically oscillating for 1 h; and (3) putting the mixed solution into a reaction kettle, carrying out hydrothermal reaction for 12h at 120 ℃, washing the pH value of the solution to 9, carrying out vacuum filtration, and drying the pumped and filtered powder for 12h at 60 ℃ to obtain a modified BN nanosheet product.

Step 3, ceramic powder modification: adding ceramic powder into ethanol and deionized water according to a volume ratio of 98: 2, carrying out ultrasonic treatment at room temperature for 15min, adding a silane coupling agent with the content of 0.38 wt%, carrying out ultrasonic oscillation for 15min, stirring for 12h, uniformly stirring and mixing, washing the product, carrying out vacuum filtration to obtain a final product, and drying the final product at 80 ℃ for 12h to obtain the modified ceramic powder product.

Step 4, preparing slurry: mixing the modified BN nanosheet with deionized water, wherein the solid content is 0.09%, and stirring for 1h to obtain BN nanosheet slurry; and simultaneously mixing the modified ceramic powder with deionized water, wherein the solid content is 0.99%, and stirring for 1h to obtain ceramic powder slurry. Then, dropwise adding the BN nanosheet slurry into the ceramic powder slurry, stirring for 1h, and ultrasonically oscillating for 60min to fully mix the BN nanosheet slurry and the ceramic powder, wherein the volume ratio of the BN nanosheet to the ceramic powder in the mixed slurry is 3: 97, preparing mixed slurry of BN nano-sheet/ceramic particles. Mixing glass powder with deionized water, wherein the solid content is 10%, stirring for 2h, and performing ultrasonic oscillation for 30min to obtain glass powder slurry.

Step 5, preparing a double-layer powder layer on the surface of the porous silicon nitride ceramic: firstly, coating the prepared mixed slurry on a pretreated porous silicon nitride ceramic substrate to form an inner powder layer; and then coating the glass powder slurry on the surface of the inner powder layer to form an outer powder layer. Then, the mixture was dried at 60 ℃ for 30min to obtain a double-layered powder layer.

And 6, sintering a sample: putting the dried sample into an atmosphere sintering furnace for sintering, wherein the sintering temperature is 1450 ℃, the heat preservation time is 1h, and the sintering atmosphere is N₂The atmosphere pressure was 0.1 MPa. The heating rate below 1000 ℃ is 15 ℃/min, the heating and cooling rates above 1000 ℃ are both 5 ℃/min, and the temperature is cooled along with the furnace after heat preservation until the temperature is cooled to the room temperature.

BNNSs/α -Si prepared in this example₃N₄the/B-Si-Al-O ceramic coating is relatively compact, and the thickness of the coating is about 100 mu m. After the coating is prepared by determination, the water absorption of the porous silicon nitride ceramic is reduced by 85 percent, the fracture toughness is obviously increased and reaches 6.02 MPa.m^1/2And after the composite coating is thermally shocked for 10 times at 1100 ℃, the coating still has good waterproof performance and mechanical property, the water absorption rate is only increased from 5.3 percent to 7.8 percent, the hardness value is 5.98GPa, the residual hardness ratio is up to 88.8 percent, and the thermal shock resistance is obviously improved.

Example 4

In this example, BNNSs/SiO was prepared on the surface of porous silicon nitride ceramic substrate₂the/Y-Si-Al-O bionic structure ceramic coating comprises the following steps:

step 1, matrix treatment: selecting porous silicon nitride with porosity of 30% as a substrate, using 600-mesh, 800-mesh and 1000-mesh sand paper to gradually and finely grind the porous silicon nitride until the surface of the substrate is smooth and flat, then putting the finely ground porous silicon nitride ceramic substrate into deionized water, ultrasonically cleaning for 15min, and drying for 12h at 70 ℃ after cleaning twice;

step 2, modifying BN nanosheets: mixing a BN nano sheet and a sodium hydroxide aqueous solution, wherein the concentration of the sodium hydroxide aqueous solution is 5mol/L, and the mass ratio of the BN nano sheet to the sodium hydroxide is 1: 20, stirring and ultrasonically oscillating for 1 h; and (3) putting the mixed solution into a reaction kettle, carrying out hydrothermal reaction for 12h at 120 ℃, carrying out vacuum filtration on the washing solution with the pH value of 9, and drying the pumped and filtered powder at 60 ℃ for 12h to obtain a modified BN nanosheet product.

Step 3, ceramic powder modification: adding ceramic powder into ethanol and deionized water according to a volume ratio of 98: 2, carrying out ultrasonic treatment at room temperature for 15min, adding a silane coupling agent with the content of 0.38 wt%, carrying out ultrasonic oscillation for 30min, stirring for 12h, uniformly stirring and mixing, washing the product, carrying out vacuum filtration to obtain a final product, and drying the final product at 80 ℃ for 12h to obtain the modified ceramic powder product.

Step 4, preparing slurry: mixing the modified BN nanosheet with deionized water, wherein the solid content is 0.09%, and stirring for 1h to obtain BN nanosheet slurry; and simultaneously mixing the modified ceramic powder with deionized water, wherein the solid content is 0.99%, and stirring for 1h to obtain ceramic powder slurry. Then, dropwise adding the BN nanosheet slurry into the ceramic powder slurry, stirring for 2 hours, and ultrasonically oscillating for 60 minutes to fully mix the BN nanosheet slurry and the ceramic powder, wherein the volume ratio of the BN nanosheet to the ceramic powder in the mixed slurry is 3: 97, preparing mixed slurry of BN nano-sheet/ceramic particles. Mixing glass powder with deionized water, wherein the solid content is 10%, stirring for 2h, and performing ultrasonic oscillation for 30min to obtain glass powder slurry.

Step 5, preparing a double-layer powder layer on the surface of the porous silicon nitride ceramic: firstly, coating the prepared mixed slurry on a pretreated porous silicon nitride ceramic substrate to form an inner powder layer; and then coating the glass powder slurry on the surface of the inner powder layer to form an outer powder layer. Then, the mixture was dried at 60 ℃ for 30min to obtain a double-layered powder layer.

And 6, sintering a sample: putting the dried sample into an atmosphere sintering furnace for sintering, wherein the sintering temperature is 1500 ℃, the heat preservation time is 1h, and the sintering atmosphere is N₂The atmosphere pressure was 0.1 MPa. The heating rate below 1000 ℃ is 15 ℃/min, the heating and cooling rates above 1000 ℃ are both 5 ℃/min, and the temperature is cooled along with the furnace after heat preservation until the temperature is cooled to the room temperature.

BNNSs/SiO prepared in this example₂the/Y-Si-Al-O ceramic coating is compact andthe interface bonding is stronger and the coating thickness is about 120 μm. After the coating is prepared by determination, the water absorption of the porous silicon nitride ceramic is reduced by 83 percent, the fracture toughness is obviously increased and reaches 6.01 MPa.m^1/2And after the composite coating is thermally shocked for 10 times at 1100 ℃, the coating still has good waterproof performance and mechanical property, the water absorption rate is only increased from 5.3 percent to 7.9 percent, the hardness value is 5.98GPa, and the thermal shock resistance is obviously improved.